JPH0668618B2 - Silver halide color negative photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a color negative photographic material, and more particularly, to a high color toner which has improved fog, decreased sensitivity, and reduced graininess after the production of the photographic material. The present invention relates to a color negative photosensitive material for sensitivity photography.

(Prior Art) In recent years, with the progress of the technology of the photosensitive material for photographing, high-sensitivity photosensitive materials have been released one after another. Expanding the shooting area by increasing the sensitivity of photosensitive materials, such as shooting without a strobe in a dark room, shooting with a high-speed shutter using a telephoto lens for sports photography, and shooting that requires long exposure such as astronomical photography Is an eternal theme imposed on the industry.

Many efforts have been made so far for increasing the sensitivity of photosensitive materials. Numerous studies have been conducted on the method of forming the shape and composition of silver halide grains, chemical sensitization, spectral sensitization, additives, coupler structures, etc., and some useful inventions have been made. However, the demand for high-sensitivity light-sensitive materials is greater than the progress of technology, and unfortunately these methods cannot be said to be sufficient. Therefore, it is a common practice in the art to make a high-sensitivity light-sensitive material by using a method of increasing the size of silver halide emulsion grains for higher sensitivity together with other techniques. Increasing the size of silver halide emulsion grains increases the sensitivity to some extent, but as long as the content of silver halide is kept constant, the number of silver halide emulsion grains inevitably decreases, and therefore There is a major drawback in that the number is reduced and the graininess is greatly impaired. In order to compensate for this drawback, two or more emulsions having the same color sensitivity and sensitivity, that is, different silver halide grain sizes, as described in British Patent No. 923,045 and Japanese Patent Publication No. 49-15495. A light-sensitive material having a layer, a method using a fast-reacting coupler as described in JP-A-55-62454, U.S. Pat.
554, so-called DIR couplers such as those described in U.S. Pat.No. 3,632,435, methods using DIR compounds, methods using couplers to produce mobile dyes described in British Patent 2,083,640, JP A method using silver halide having a high average silver iodide content described in JP-A-60-128443 is known. Each of these methods is an excellent invention that has a great effect, but it is not a sufficient technology for the great demand for high sensitivity and high image quality. Therefore, in order to increase the grain size of silver halide emulsion grains and at the same time increase the number of development start points, various properties such as desilvering property during bleach-fix processing are allowed for high-sensitivity color negative photosensitive materials. Designs have been made with a high content of silver halide emulsion grains in the range.

On the other hand, it has been known to change the positions of layers of a color negative photosensitive material composed of multiple layers in order to realize high sensitivity in a high sensitivity color negative photosensitive material or to achieve both high sensitivity and high image quality. For example, U.S. Pat.Nos. 4,184,876 and 4,1
29,446, 4,186,016, British Patent 1,560,965, U.S. Patent 4,186,011, 4,267,264, 4,173,479.
No. 4,157,917, 4,165,236, British Patent No. 2,138,
962, JP-A-59-177,552, British Patent No. 2,137,372
No. 59-180,555, 59-180,556, 59-
No. 204,038, etc.

In these techniques, as described in JP-A-59-177,552, the emulsion layer on the side closer to the support causes the loss of the exposure amount and the delay of development due to the influence of the emulsion layer on the side farther from the support. It is known that the emulsion becomes less and softer, so that the most sensitive emulsion layer of each of the red-sensitive emulsion layer and / or the green-sensitive emulsion layer, which is located closer to the support than usual, is as far as possible from the support. It is intended to achieve high sensitivity by locating in the position.

[Problems to be solved by the invention]

By the way, it has been found that when the positions of the layers of the color negative light-sensitive material composed of multiple layers are changed to improve the sensitivity, the following disadvantages are unfavorable. By arranging the emulsion layer with the highest sensitivity on the side farther from the support, the loss of exposure and the delay in development received by the emulsion layer with the lower sensitivity located on the side closer to the support are increased, and If the grain size of silver halide grains in the emulsion layer of sensitivity is increased and the content thereof is not increased, the gradation and maximum density required for the light-sensitive material cannot be maintained. As a result, disadvantages such as increased cost, desilvering and poor fixability were born. Other than that, it is probably because the grain size of the low-sensitivity emulsion layer was increased, but the graininess was worse than expected, and as described below, fog increased during the storage period before production and after use. It was also found that the deterioration of the photographic performance of

(Object of the Invention) An object of the present invention is, firstly, to provide a high-sensitivity color negative photosensitive material having a high image quality, and secondly, at a low cost, with a high image-sensitivity having a high desensitization property. The third object is to provide a color negative light-sensitive material, and thirdly to provide a high-sensitivity color negative light-sensitive material in which performance deterioration such as increase in fog during storage after production is minimized.

[Means for solving problems]

The present invention comprises a support having a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler. , Specific photo sensitivity is 32
In the color negative light-sensitive material of 0 or more, the content of all silver contained in the light-sensitive material is 3.0 g / m ^{2 to} 9.0 g / m ² , and the red-sensitive emulsion layer, the green-sensitive emulsion layer, And each of the blue-sensitive emulsion layers are composed of two or more emulsion layers having different sensitivities, that is, the most sensitive red-sensitive emulsion layer, the most sensitive green-sensitive emulsion layer, and the most sensitive blue-sensitive emulsion layer. At least one emulsion layer having a different color sensitivity from the highest sensitivity layer closest to the support is located between the layer closest to the support and the red sensitivity emulsion layer having the highest sensitivity, Each of the most sensitive green-sensitive emulsion layer and the most sensitive blue-sensitive emulsion layer contains a 2-equivalent fast-reacting cyan coupler, a 2-equivalent fast-reactive magenta coupler, and a 2-equivalent fast-reactive yellow coupler. Silver halide color characterized by It was achieved by gas-sensitive material.

Hereinafter, the present invention will be described in detail.

In the present invention, the specific photographic sensitivity as detailed and defined below is adopted as the sensitivity of the photographic light-sensitive material for the following reasons.

That is, the sensitivity of photographic light-sensitive materials is generally an international standard.
Although ISO sensitivity is used, in ISO sensitivity, the photosensitive material is developed on the 5th day after exposure, and the development processing is specified by each company. The following specific photographic speeds were adopted so as to shorten the time (0.5 to 6 hours) and to carry out a constant development process.

The specific photographic speed of the light-sensitive material in the present invention is determined according to the following test method according to ISO speed.
(According to JIS K 7614-1981) (1) Test conditions The test is carried out in a room at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%. The photosensitive material to be tested is left in this state for 1 hour or more before use.

(2) Exposure The relative spectral energy distribution of the reference light on the exposed surface shall be as shown in Table 1.

The illuminance change on the exposed surface is performed by using an optical wedge. The optical wedge to be used has a spectral transmission density fluctuation of 360% to 700 nm in any part, within 10% in a region of less than 400 nm, and within 5% in a region of 400 nm or more. Use the one.

The exposure time is 1/100 second.

(3) Development processing From exposure to development processing, the photosensitive material to be tested is kept at a temperature of 20 ± 5 ° C and a relative humidity of 60 ± 10%.

The development process is completed within 30 minutes to 6 hours after exposure.

Development processing is performed as follows.

1. Color development ………… 3 minutes 15 seconds, 38.0 ± 0.1 ℃ 2. Bleach ……………… 6 minutes 30 seconds, 38.0 ± 3.0 ℃ 3. Washing ……………… 3 minutes 15 seconds, 24〜 41 ℃ 4.Fixing ……………… 6 minutes 30 seconds, 38.0 ± 3.0 ℃ 5.Washing ……………… 3 minutes 15 seconds, 24-41 ℃ 6.Stable ……………… 3 minutes 15 Second, 38.0 ± 3.0 ℃ 7. Drying ………… 50 ℃ or below The composition of the processing liquid used in each process is shown below.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5g Water added 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0 pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0m Sodium bisulfite 4.6g Water added 1.0 pH 6.6 Stable Liquid Formalin (40%) 2.0m Polyoxyethylene-p-monononylphenyl ether (flat Polymerization degree: 10) was added to 0.3g Water to make 1.0 (4) Concentration measured concentration is expressed in _{log 10 (Φ 0 / Φ)} . Φ ₀ is an illumination light flux for density measurement, and Φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction, and the standard is to use the total light flux that is transmitted as a transmitted light flux and diffused in a half space, and standard when other measurement methods are used. Correct with density strips. In addition, the emulsion film surface shall face the light-receiving device side during measurement. Density measurement is performed with blue, green, and red status M densities, and their spectral characteristics are set to values shown in Table 2 as comprehensive characteristics of the light source, optical system, optical filter, and light receiving device used in the densitometer.

(5) Determination of specific photographic sensitivity The specific photographic sensitivity is determined by the following procedure using the results of processing and density measurement under the conditions shown in (1) to (4).

Blue, green, red, for the minimum concentration of each of the respective H _B represents an exposure amount corresponding to 0.15 higher concentrations lux · _sec, H G, _{and H R.}

H _B, the larger value out of the _{H R} (the lower sensitivity) H
_S.

The specific photographic sensitivity S is calculated according to the following formula.

In a high-sensitivity color negative light-sensitive material, as described above, and as described in, for example, JP-A-58-147744, the content of silver halide emulsion grains should be minimized in order to improve the graininess as much as possible. Many designs have been the practice of the industry so far. In a color negative light-sensitive material, an emulsion layer having the same color sensitivity is used with different sensitivities.
It is a common sense to obtain a high-quality color negative light-sensitive material by designing the emulsion layer having a higher sensitivity to increase the silver content in order to utilize the so-called grain disappearing effect when it is composed of more than one emulsion layer. there were.

However, when we try to obtain high image quality and high sensitivity by using the technique described above, in which the high-sensitivity emulsion layer of the multi-layer color negative photosensitive material is located as far as possible from the support, it is surprising. In particular, he found that this common sense did not apply. It is considered that if the silver content of the higher sensitivity emulsion layer is too high, the sensitivity and image quality of the lower sensitivity emulsion layer closer to the support will be impaired. It is difficult to achieve both image quality. Rather, it is better to reduce the silver content in the layer of higher sensitivity to reduce the silver content, especially in combination with the layer position of the above-mentioned multilayer color negative photosensitive material. You can make materials. Naturally, the color negative light-sensitive material produced in this manner is low in manufacturing cost, and is also excellent in desilvering and fixing property during development processing. Further, it has been surprisingly found that deterioration of photographic performance such as increase in fog, deterioration of sensitivity, deterioration of graininess, etc. which occurs during the storage period after production after use is unlikely to occur. This is probably due to the effect of natural radiation as described in JP-A-63-226650.

The content of silver contained in the color negative photosensitive material of the present invention is
It must be 3.0g / m ² or more and 9.0g / m ² or less. It is preferably 3.0 g / m ² or more and 8.5 g / m ² or less, more preferably 3.0 g / m ² or more and 8.0 g / m ² or less.

The content of silver in the most sensitive emulsion layer of each of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer is preferably 0.3 g / m ² or more and 1.8 g / m ² or more.
more preferably m ² and more preferably not more than 0.3 g / m ² or more 1.6 g / m ² or less is 0.3 g / m ² or more 1.4 g / m ² or less.

Several methods are known for analyzing the silver content of the light-sensitive material, and any method may be used. For example, elemental analysis using fluorescent X-rays is easy.

The specific photographic sensitivity of the color negative photographic material of the present invention must be 320 or more. In the case of lower sensitivity, the effect of the combination of the arrangement of the layers of the multilayer color negative light-sensitive material of the present invention with the amount of silver contained is not sufficiently exerted. Preferably 400 or more, more preferably 8
00 or more.

The color negative photographic material of the present invention comprises a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer, each of which is composed of two or more emulsion layers having different sensitivities. At least one emulsion layer having a different color sensitivity from the highest sensitivity layer closest to the support is located between the support and the layer closest to the support among the sensitive emulsion layer and the blue sensitivity emulsion layer having the highest sensitivity. There is a need to.

Further, it is more preferable that each color-sensitive layer has a three-layer structure in order to further improve the graininess. This technique is described in Japanese Examined Patent Publication No. 49-15495.

A non-photosensitive layer may be present between each photosensitive emulsion layer. This non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. When light-sensitive emulsion layers having different color sensitivities are adjacent to each other, it is preferable to provide a non-light-sensitive layer between them. Such a non-photosensitive intermediate layer may contain a scavenger substance. In addition, JP-A-59-160,
It is also preferred to provide a non-light sensitive reflective layer under the light sensitive emulsion layer to improve sensitivity as described in JP-A-135.
The color negative light-sensitive material of the present invention usually contains a yellow filter layer, though it is not always necessary.

Specific examples of the order of arranging the light-sensitive emulsion layers in the color negative light-sensitive material of the present invention are shown below, but the order is not limited thereto. Although the non-photosensitive layer is omitted here, it may be present at the position as described above.

(1) Support, low-sensitivity red-sensitive emulsion layer (hereinafter RL), low-sensitivity green-sensitive emulsion layer (hereinafter GL), low-sensitivity blue-sensitive emulsion layer (hereinafter B)
L), high-sensitivity red-sensitive emulsion layer (RH), high-sensitivity green-sensitive emulsion layer (GH), high-sensitivity blue-sensitive emulsion layer (BH).

(2) Support, RL, GL, BL, GH, RH, BH (3) Support, RL, GL, BL, RH, intermediate green sensitive emulsion layer (hereinafter G
M), GH, BH (4) support, RL, GL, GM, BL, RH, GH, BH (5) Support RL, intermediate red sensitive emulsion layer (hereinafter RM), GL, GM, B
L, intermediate blue sensitive emulsion layer (BM), RH, GH, BH (6) support, RL, GL, BL, RM, RH, GM, GH, BM, BH (7) support, RL, GL , RH, GH, BL, BH (8) support, GL, RL, RH, GH, BL, BH (9) support, RL, GL, RH, GM, GH, BL, BH (10) support, RL, GL, GH, RH, BL, BH In the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and Any of silver chloride may be used. A preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 2 to 20 mol% of silver iodide. In order to achieve both high sensitivity and high image quality, the average silver iodide content of silver halide in all emulsion layers should be 8 mol% or more as described in JP-A-60-128,443. Is preferred. It is known that if the average silver iodide content of silver halide is increased, the graininess is remarkably improved. However, when the silver iodide content exceeds a certain level, the development speed delay, desilvering and fixing speed Defects such as delay come out. However, in the present invention, it is probably because the content of silver contained is small, but even if the silver iodide content is increased, these drawbacks are less likely to cause a problem and are very preferable.

The silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention are composed of a core consisting essentially of silver iodobromide containing 5 mol% or more of silver iodide, and a core covering the core. It is preferable to have a double structure composed of a silver iodobromide or a shell consisting essentially of silver bromide having a silver iodide content lower than that of the core. The silver iodide content of the core is more preferably 10 mol% or more, and most preferably 20 mol% or more and 44 mol% or less. The silver iodide content of the shell is preferably 5 mol% or less.

The core may contain silver iodide uniformly, or may have a multiple structure composed of phases having different silver iodide contents. In the latter case, the silver iodide content of the phase having the highest silver iodide content is 5 mol% or more, more preferably 10 mol% or more, and the silver iodide content of the shell is the core. It is better if it is lower than that of the highest silver iodide content phase. or,
The phrase "consisting essentially of silver iodobromide" means that it is mainly composed of silver iodobromide, but other components may be contained up to about 1 mol%.

As a more preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, a silver halide grain having a diffraction angle (2θ) of 38 to 42 ° and using Cu Kβ rays is used. When the curve of the diffraction intensity vs. diffraction angle of the (220) plane is obtained, two diffraction maxima, a diffraction peak corresponding to the core part and a peak corresponding to the shell part, and one minimum appears between them, and the core It is a particle having a structure in which the diffraction intensity corresponding to the portion is 1/10 to 3/1 of that of the shell portion. Particularly preferably, the diffraction intensity ratio is 1/5 to 3 /
1 and 1/3 to 3/1.

With such a double structure, it is possible to use a high iodine silver iodobromide emulsion without delaying the development speed, and to achieve a light-sensitive material having excellent graininess even with a small amount of coated silver. You can

The average grain size of silver halide grains in a photographic emulsion (the grain diameter in the case of spherical grains or grains close to spheres, the edge length in the case of cubic grains is the grain size, and is represented by the average based on the projected area). Although not particularly limited, it is preferably 0.05 μm or more and 10 μm or less. The average size of silver halide grains in each emulsion layer having the highest sensitivity is preferably 0.5 μm or more and 4 μm or less, more preferably 0.6 μm or more and 2.5 μm or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubes and octahedra, and spherical,
Those having an irregular crystal body such as a plate shape, or a composite form of these crystal forms may be used. It may consist of a mixture of particles of various crystal forms.

Further, it is preferable to use tabular grains having a high color sensitizing efficiency with a sensitizing dye and having an aspect ratio of 5 or more.

Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photographic S
cience and Engineering), Volume 14, pp. 248-257 (1970
Year); U.S. Pat. Nos. 4,434,226, 4,414,310, and 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157.

The photographic emulsion used in the present invention is described by P. Glafkides, Chimie et.
Physique Photographique (Published by Paul Montel, 1967
), GF Duffin Photographic Emulsion Chemistry
(Published by The Focal Press, 1966) by VL Zelikman et al
Making and Coating Photographic Emulsion (The Foca
l Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Good.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
Can also be used, that is, a so-called controlled double jet method can be used.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion used in the present invention has a crystal plane defined by the Miller index (nn1) (n ≧ 2, n is a natural number) on the outer surface as described in JP-A-86-9598. A silver halide grain having is preferably used.

Further, a silver halide emulsion having a hollow conductive portion from the surface to the inside as described in JP-A-61-75337 is also preferably used. Such a silver halide emulsion having a large specific surface area is more effective when used in combination with the present invention because it is more likely to give a higher sensitivity than an emulsion having the same volume, especially when color sensitized.

Further, JP-A-57-133540, JP-A-58-108526 or JP-A-57-133540
Composite particles in which silver salts having different compositions are epitaxially grown on host particles as described in 59-162540 can be preferably used in the present invention. Such particles are preferable in combination with the present invention because they exhibit high hardness and high photographic properties.

Further, silver halide emulsions grown in the presence of tetrazaindene as described in JP-A-61-146030 and JP-A-60-122935 have high silver iodide content and excellent monodispersity. Therefore, since it exhibits high sensitivity and excellent graininess, it is preferably used as a silver halide emulsion used in the present invention.

Further, as disclosed in JP-A-58-126526, a silver halide emulsion sensitized by gold sulfur or gold selenium in the presence of a nitrogen-containing heterocyclic compound exhibits high fog sensitivity and high sensitivity. Therefore, it is preferably used as a silver halide emulsion used in the present invention.

The slightly rounded cubic or tetradecahedral crystals described in JP-A-59-149345 or 59-149344 are silver halide emulsions used in the present invention because they have high sensitivity. Is preferred as

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together.

Of these, silver halide emulsions formed in the presence of iridium have high sensitivity (Japanese Patent Publication No.
And JP-B-45-32738), and particularly preferred as the silver halide emulsion used in the present invention.

Emulsions are usually freed from soluble salts after precipitation or physical ripening. As a means therefor, the Nudel water washing method, which is a known method of gelling gelatin, may be used. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulphonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin) The sedimentation method (flocculation) described above may be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, “Die Grundlagender” edited by H. Frieser.
Photographischen Prozesse mit Silber-halogeniden "
(Akademische Verlagsgesellchaft, 1968) 675 to 734 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, first tin salt, Reduction sensitization using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds; noble metal compounds (eg, gold complex salts, etc.)
A noble metal sensitization method using a complex salt of a metal of Group VIII of the Periodic Table such as Pt, Ir, Pd and the like can be used alone or in combination.

Further, it is preferable to use a selenium sensitizing method using a compound containing selenium capable of reacting with active gelatin or silver in combination with another sensitizing method because a high sensitivity emulsion can be obtained. This technology is disclosed in U.S. Pat.Nos. 1,574,944, 1,602,592, 1,623,
Japanese Patent Publication No. 499, Japanese Patent Publication No. 52-38408, Japanese Patent Publication No. 57-22090, Japanese Patent Publication No. 59-180536, US Pat.
-185329 and JP-A-60-150046.

The photographic emulsion used in the present invention is spectrally sensitized with a methine dye or the like, if necessary. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine nuclei, indole nuclei, benzoxadol nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thiooxazoline gin-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or thiobarbituric acid nucleus can be applied.

Examples of useful sensitizing dyes include German Patent 929,080.
U.S. Patents 2,231,658, 2,493,748, 2,503,77
No. 6, No. 2,519,001, No. 2,912,329, No. 3,656,959,
No. 3,672,897, No. 3,694,217, No. 4,025,349, No. 4,0
46,572, British Patent 1,242,588, Japanese Patent Publication No. 44-14030,
The one described in No. 52-24844 can be mentioned.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example is a US patent
2,688,545, 2,977,229, 3,397,060, 3,52
2,052, 3,527,641, 3,617,293, 3,628,964
No., No. 3,666,480, No. 3,672,898, No. 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
No. 507,803, Japanese Patent Publication No. 43-4936, No. 53-12375, Japanese Patent Laid-Open No.
Nos. 52-110618 and 52-109925.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Aminostil compounds substituted with nitrogen-containing heterocyclic groups) such as those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), and cadmium salts ,
An azaindene compound or the like may be included. US Patent 3,61
5,613, 3,615,641, 3,617,295, 3,635,721
The combinations described in item No. are particularly useful.

A color coupler is added as a dye image-forming substance to the photographic emulsion layer used in the present invention.

It is common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Also, U.S. Pat.No. 3,497,350 or JP-A-59-214853.
It is also possible to use a method in which the color sensitivity of the emulsion layer and a color image-forming coupler are appropriately combined as described in JP-A No. 1994-242, and this layer is provided at a position farthest from the support.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides,
Pivaloyl acetanilides) and the like, and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule or polymerized ones. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions, but in order to reduce the content of silver contained in the light-sensitive material, a 2-equivalent coupler having higher silver utilization efficiency should be used. It is preferable to use. In the present invention, a 2-equivalent fast-reacting cyan coupler and a 2-equivalent high-speed emulsion as described below are added to the most sensitive emulsion layers of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer, respectively. A reactive magenta coupler and a 2-equivalent fast-reacting yellow coupler are contained, respectively.

The coupling reactivity of the coupler is determined by mixing two types of couplers M and N which give different dyes which can be clearly separated from each other, and adding them to the emulsion to develop a color image. It can be determined as a relative value by measuring the dye amount.

The maximum density of the coupler M (DM) max., The color of the density DM in the middle stage, and that of the coupler N (D
Assuming that N) max., DN is developed, the reaction activity ratio RM / RN of both couplers is expressed by the following equation.

In other words, several emulsions containing mixed couplers are exposed to light at various stages, and several DM and DN pairs obtained by color development are made into two orthogonal axes. The coupling activity ratio RM / RN is obtained from the slope of the straight line obtained by plotting.

If the value of RM / RN is obtained as described above for various couplers using a fixed coupler N, the coupling reactivity is relatively obtained. The coupler N may be obtained by using, for example, the following coupler.

For cyan coupler For magenta coupler and yellow coupler As the fast-reacting coupler used in the present invention, the value of RM / RN obtained using the above-mentioned coupler N has a value of 1.5 or more in the case of a cyan coupler, 2.5 or more in the case of a magenta coupler, and 1 in the case of a yellow coupler. Each is preferred.

Specific examples of the two-equivalent high-speed reaction couplers used in the present invention are shown below, but the present invention is not limited thereto.

Cyan coupler example Magenta coupler example Yellow coupler example In the present invention, such a fast-reacting coupler is added to at least the most sensitive unit emulsion layer of each color-sensitive layer. There are no particular restrictions on the amount used, but cyan fast coupler 0.005 to 0.1, magenta fast coupler 0.005 to 0.1, and yellow fast coupler 0.001 per mol of silver.
A range of 5 to 0.1 is preferred.

Further, in the present invention, a non-diffusive coupler in which the formed dye defined in US Pat. No. 4,420,556 (1) and (3) to (8) and JP-A-59-191036 has a suitable diffusivity. It is preferable to improve the sensitivity by improving the covering power and improve the graininess. These couplers are disclosed in the above-mentioned patents and JP-A-56-1938.
No. 57-3934, No. 53-105226, U.S. Pat.
It can be easily synthesized according to the method described in No. 723 and the like.

In the present invention, in addition to the above-mentioned coupler, a colored coupler having a color correcting effect or a coupler (so-called DIR coupler) which releases a development inhibitor upon development may be used.

Further, in addition to the DIR coupler, a colorless DIR coupling compound which is colorless as a product of the coupling reaction and releases a development inhibitor may be contained.

In the present invention, it is preferable to achieve high sensitivity by using a compound (hereinafter referred to as FR compound) capable of forming a development accelerator or a fogging agent with silver development. These FR compounds are described in U.S. Patent Nos. 4,390,618, 4,518,682 and 4,526,
No. 863, No. 4,482,629, JP-A Nos. 59-157638 and 59-17.
It can be easily synthesized by the methods described in 0840, 60-185950, 60-1007029 and the like.

Two or more FR compounds may be used in combination. The amount of FR compound added is 0.2 mol or less per 1 mol of silver in the same layer or adjacent layers 1
0 ^-10 mol or more, preferably 0.02 mol or less 10 ^-7 mol. The FR compound can be used alone or in combination with the coupler for forming a color image by introducing it into the silver halide emulsion layer by an oil-in-water dispersion method known as an oil protect method, to achieve the intended purpose. .

The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl citrate) ), Benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyllaurylamide), fatty acid ester (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid ester (eg tributyl trimesate)
Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After being dissolved in methyl cellosolve acetate or the like, it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The photographic color developer used is conveniently chosen to give an intermediate scale image. Cyan dyes formed from cyan colorants have a maximum absorption band between about 600 and about 720 nm, magenta dyes formed from magenta colorants have a maximum absorption band between about 500 and 580 nm, and yellow colorants The maximum absorption band of the yellow dye formed from is preferably between about 400 and 480 nm.

The light-sensitive material of the present invention may contain a dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patents 584,609 and 1,77,429.
No. 48-85130, No. 49-99620, No. 49-114420
No. 52-108115, U.S. Patents 2,255,077, 2,274,7.
No. 82, No. 2,390,707, No. 2,493,747, No. 2,533,472
No. 2, No. 2,843,486, No. 2,956,879, No. 3,148,187,
3,177,078, 3,247,127, 3,540,887, 3,5
75,704, 3,653,905, 3,718,472, 4,071,31
No. 2, No. 4,070,352, No. 4,420,555.

In the light-sensitive material of the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like. For example, U.S. Pat.Nos. 685,475, U.S. Pat.
9,401, 2,882,156, 3,048,487, 3,184,309
No. 3,445,231, West German patent application (OLS) 1,914,362
The polymers described in JP-A Nos. 50-47624 and 50-71332 can be used.

Various additives generally used in silver halide light-sensitive materials can be used in the light-sensitive material of the present invention. Such materials are described, for example, in US Pat. No. 4,599,301. A typical example is the same specification, column 33, 12
From line 38 column 45 line 45 surfactant (column 33), water-insoluble or sparingly soluble polymer (column 33-34), ultraviolet absorber (column 37-38), color antifoggant (column 37), Color fogging inhibitors (column 38), hydroquinones (column 38), etc.

The light-sensitive material of the present invention is, for example, the above-mentioned US Pat. No. 4,599,301.
The development processing is carried out according to the method described in columns 34 to 35 of the specification.

Next, specific processing steps applicable to the color light-sensitive material of the present invention are shown below, but the present invention is not limited to these.

1. Color development-bleach- (wash) -fixing- (wash)-(stable) 2. Color development-bleach-fix- (wash)-(stable) 3. Color development-bleach-bleach-fix- (wash)-( Stable) 4. Color development-bleach-bleach-fix-fix- (wash)-(stable) 5. Color development-bleach-fix-bleach-fix- (wash) -black and white-wash- (reverse) -Color development- (Adjustment) -Bleach-Fixing- (Washing)-(Stable) 7. Black and white development-Water washing- (Reversal) -Color development- (Adjustment) -Bleach fixing- (Water washing)-(Stable) 8. Black and white Development-water washing- (reversal) -color development- (adjustment) -bleaching-bleach-fixing- (water washing)-(stable) The steps marked with () can be omitted depending on the type, purpose and use of the light-sensitive material. Washing and stabilization cannot be omitted at the same time.

Hereinafter, the treatment bath will be described.

Color Development The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β
-Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, tetraphenylborate, p- (t-octyl) benzenesulfonate and the like. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

Examples of aminophenol derivatives include o-aminophenol, p-aminophenol, 4-amino-2-
Methylphenol, 2-amino-3-methylphenol, 3-oxy-3-amino-1,4-dimethylbenzene and the like are included.

In addition, LFA Meson's "Photographic Processing Chemistry", Focal Press (1966
(LFAMason, “Photographic Processing Chemist
ry ", Focal Press) pp. 226-229, U.S. Pat. No. 2,193,015
Nos. 2,592,364 and JP-A-48-64933 may be used. If desired, two or more color developing agents may be used in combination.

Color developers include pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Hydroxylamine, triethanolamine, compounds described in West German Patent Application (OLS) No. 2622950, preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary Development accelerators such as ammonium salts, amines, thiocyanates, 3,6-thiaoctane-1,8-diols; dye-forming couplers; competing couplers; nucleating agents such as sodium boron hydride; 1-phenyl-3 -Auxiliary developing agents such as pyrazolidone, tackifiers; ethylenediaminetetraacetic acid, nitrilo Acetate, cyclohexane diamine tetraacetic acid, iminodiacetic acid, N- hydroxymethyl diamine triacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and, JP 58-195845
Aminopolycarboxylic acids represented by the compounds described in No. 1-hydroxyethylidene-1,1'-diphosphonic acid, Research Disclosure 18170 (May 1979)
Aminophosphonic acids such as organic phosphonic acids, aminotris (methylenephosphonic acid), ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, etc.
No. 102726, No. 53-42730, No. 54-121127, No. 55-4
No. 024, No. 55-4025, No. 55-126241, No. 55-65955
Nos. 55-65956, and Research Disclosure 18170 (May 1979).

The color developing agent is generally about 0.1 per 1 color developing solution.
To about 30 g, more preferably about 1 g to about 15 g per color developer. Also, p of the color developing solution
H is usually 7 or more, and is most commonly used from about 9 to about 13. Further, the replenishing amount can be reduced by using a replenishing solution in which the concentrations of halides, color developing agents and the like are adjusted as the color developing solution.

The processing temperature of the color developer of the present invention is preferably 20 to 50 ° C, more preferably 30 to 40 ° C. Processing time is 20 seconds ~
It is preferably 30 seconds to 5 minutes, more preferably 10 minutes.

Bleaching solution, bleach-fixing solution, fixing solution As a bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, a ferric ion complex is a ferric ion and aminopolycarboxylic acid, aminopolyphosphonic acid or those. It is a complex with a chelating agent such as a salt. The aminopolycarboxylic acid salt or aminopolyphosphonic acid salt is a salt of aminopolycarboxylic acid or aminopolyphosphonic acid with an alkali metal, ammonium, or a water-soluble amine. The alkali metal is sodium, potassium, lithium, etc., the water-soluble amine is methylamine,
Examples are alkylamines such as diethylamine, triethylamine and butylamine, finger-ring amines such as cyclohexylamine, arylamines such as aniline and m-toluidine, and heterocyclic amines such as pyridine, morpholine and piperidine.

Typical examples of these chelating agents such as aminopolycarboxylic acid and aminopolyphosphonic acid or salts thereof are ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, and elerenediaminetetraacetic acid tetra (trimethylammonium) salt. Salts Ethylenediaminetetraacetic acid tetrapotassium salt Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid ethylenediamine-N- (β-oxyethyl) -N, N ',
N'-Triacetic acid trisodium salt Ethylenediamine-N- (β-oxyethyl) -N, N ',
N'-Triacetic acid triammonium salt 1,2-Diaminopropane tetraacetic acid 1,2-Diaminopropane tetraacetic acid disodium salt 1,3-Diaminopropane tetraacetic acid 1,3-Diaminopropane tetraacetic acid diammonium salt Nitrilotriacetic acid Nitrilotriacetic acid Trisodium salt Cyclohexanediaminetetraacetic acid Cyclohexanediaminetetraacetic acid disodium salt Iminodiacetic acid Dihydroxyethylglycine Ethyletherdiaminetetraacetic acid Glycoletherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Phenylenediaminetetraacetic acid 1,3-diaminopropanol-N, N, N ' , N'-tetramethylenephosphonic acid Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1,3-propylenediamine-N, N, N', N'-tetramethylenephosphonic acid, etc. However, the compounds are not limited to these exemplified compounds.

In general, among the above chelating agents, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and 1,3-diaminopropanetetraacetic acid are preferable.

The ferric ion complex salt may be used in the form of a complex salt.
Iron salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc., and chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. May be used to form a ferric ion complex salt in a solution. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one or more ferric salts may be used. Furthermore, one or more chelating agents may be used. Further, in any case, the chelating agent may be used in an amount more than that for forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complex is preferable, and the addition amount thereof is 0.1 to 1 mol /, preferably 0.2 to 0.4 mol / in a bleaching solution of a color photographic light-sensitive material for photographing such as a color negative film. In the bleach-fixing solution, it is 0.05 to 0.5 mol /, preferably 0.1.
~ 0.3 mol /. In a bleaching solution or a bleach-fixing solution for a color photographic light-sensitive material for printing such as color paper, the amount is 0.03 to 0.3 mol / m, preferably 0.05 to 0.2 mol / m.

Further, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent 1,290,8.
No. 12, No. 2,059,988, JP-A No. 53-32736, No. 53-5783
No. 1, No. 37418, No. 53-65732, No. 53-72623, No. 53
-95630, 53-59631, 53-104232, 53-12
No. 4424, No. 53-141623, No. 53-28426, Research
Compounds having a mercapto group or a disulfide group described in Disclosure No. 17129 (July 1978), etc .; Thiazolidine derivatives as described in JP-A-50-140129; JP-B-45-8506, JP-A-SHO 52-20832,
No. 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, iodide described in JP-A-58-16235; polyethylene described in West German Patents 966,410, 2,748,430. Oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434
No. 49, No. 59644, No. 53-94927, No. 54-35727,
The compounds described in JP-A-55-26506 and JP-A-58-163940, iodine, bromide ion and the like can be mentioned. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat.
Compounds described in 858, West German Patent 1,290,812 and JP-A-53-95630 are preferable.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, iodide). Ammonium) rehalogenating agents can be included. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Addition of one or more inorganic acids, organic acids and their alkali metal or ammonium salts having pH buffering ability such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc., or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can do.

The bleach-fixing solution of the present invention or the fixing agent used in the fixing solution is
Known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; thioether compounds such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas. 1
One kind or a mixture of two or more kinds can be used. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-51-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

The amount of the fixing agent per 1 is preferably 0.3 to 2 moles, particularly 0.8 to 1.5 moles in the processing of color photographic light-sensitive materials for photographing, and in the processing of color photographic light-sensitive materials for printing.
It is in the range of 0.5 to 1 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is 3 to 10
Is preferable, and 5-9 is particularly preferable. When the pH is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stin is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution and the fixing solution of the present invention include a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as a preservative. , Metabisulfite (eg potassium metabisulfite,
Sodium metabisulfite, ammonium metabisulfite,
Etc.) and the like. These compounds are about 0.02-0.50 mol / calculated as sulfite ion
It is preferable to contain, more preferably 0.04 to 0.
40 mol /

As a preservative, it is common to add sulfite, but in addition, ascorbic acid and carbonyl bisulfite adduct,
Alternatively, a carbonyl compound or the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent, etc. may be added as required.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering processing such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and Television Engineers (Journ
al of the Society of Motion Picture and Television
Engineers) Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above document, the amount of washing water can be greatly reduced, and for example, the replenishment amount per unit area of the light-sensitive material can be 1 to 50 times the carry-in amount from the previous bath, but in the tank. The increase in the residence time of water in the above causes problems such as the propagation of bacteria and the adherence of the produced floating substances to the light-sensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542,
Chlorinated germicide such as chlorinated sodium isocyanurate,
Others such as benzotriazole, Hiroshi Horiguchi "Chemistry of antibacterial and antifungal agents", Hygiene Technology Association, "Sterilization, sterilization, antifungal technology of microorganisms", Japan Antibacterial and Antifungal Society, "Encyclopedia of antibacterial and antifungal agents", It is also possible to use the bactericide described in.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of seconds to 5 minutes is selected.

Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543, 58-14834, 59-184
343, 60-220345, 60-238832, 60-239784, 6
All known methods described in 0-239749, 61-4054, 61-118749 and the like can be used.

Particularly, a stabilizing bath suitable for the color light-sensitive material of the present invention includes 5-chloro-2-methyl-4-isothiazoline-3.
Those containing a chelating agent such as -one, a surfactant, formalin, and ethylenediaminetetraacetic acid are preferable.

Further, a method of performing these stabilizing treatments after the above-mentioned water washing treatment is also widely practiced.

Surfactants in the stabilizing bath may not only prevent unevenness of water droplets during drying but also promote cleaning of the components in the light-sensitive material, and these surfactants include polyethylene glycol type nonionic surfactants, A polyhydric alcohol type nonionic surfactant is preferable, and an alkylphenol ethylene oxide adduct is particularly preferable. The alkylphenol is particularly preferably octyl, nonyl, dodecyl or dinonylphenol, and the addition mole number of ethylene oxide is particularly preferably 8 to 14 moles.

The stabilizing bath is used by adjusting the pH to 3-8. For adjusting the pH, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, mineral acids such as sulfuric acid and hydrochloric acid,
Organic acids such as acetic acid, tartaric acid, citric acid can be used.

〔Example〕

 Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 On a subbed cellulose triacetate film support,
A sample, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) First layer (antihalation layer) Black colloidal silver 0.3 Gelatin 1.0 UV absorber UV-1 0.1 Same as above UV-2 0.1 Same as above UV-3 0.1 Same as above UV-2 0.1 Dispersed oil Oil-1 0.2 Same as above Oil -2 0.1 Second layer (intermediate layer) Gelatin 1.0 Colored coupler C-2 0.02 Dispersion oil Oil-1 0.01 Third layer (low-sensitivity red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, Average grain shape 1.0
μ) 1.8 Sensitizing dye I 1.4 × 10 ^-4 Sensitizing dye II 7 × 10 ^-5 Coupler C-1 0.5 Coupler C-2 0.05 Dispersion oil Oil-3 0.03 Dispersion oil Oil-4 0.03 4th layer (intermediate layer) Gelatin 1.0 Compound A 0.1 Fifth layer (low-sensitivity green sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain form 1.0
μ) 1.4 〃 (3 mol% silver iodide, average grain size 0.3)
μ) 0.3 Gelatin 0.8 Sensitizing dye III 3 × 10 ^-4 Sensitizing dye IV 1 × 10 ^-4 Sensitizing dye V 1 × 10 ^-4 Coupler C-3 0.7 Coupler C-4 0.1 Coupler C-5 0.1 Dispersion oil Oil -3 0.1 Sixth layer (intermediate layer) Gelatin 1.0 Compound A 0.1 Seventh layer (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain form 1.0)
μ) 0.7 〃 (3 mol% silver iodide, average grain size 0.3
μ) 0.2 Gelatin 1.0 Sensitizing dye VI 2 × 10 ^-4 Sensitizing dye VII 2 × 10 ^-4 Coupler C-6 0.6 Coupler C-10 0.6 Dispersion oil Oil-1 0.1 Eighth layer (intermediate layer) Gelatin 1.0 Compound A 0.1 9th layer (high-sensitivity red-sensitive emulsion layer) Percentage silver iodobromide emulsion (silver iodide 6 mol%, average grain shape 2.0)
μ) 2.3 Gelatin 1.2 Sensitizing dye I 7 × 10 ⁻⁵ Sensitizing dye II 2 × 10 ⁻⁵ Coupler C-8 0.1 Coupler C-1 0.2 Dispersion oil Oil-4 0.2 10th layer (intermediate layer) Gelatin 1.0 Coupler C -5 0.2 Compound A 0.1 11th layer (high-sensitivity green-sensitive emulsion layer) Percentage silver iodobromide emulsion (5 mol% silver iodide, average grain shape 2.0)
μ) 2.0 Gelatin 1.0 Coupler C-9 0.2 Dispersion oil Oil-1 0.4 12th layer (intermediate layer) Fine grain silver bromide emulsion (average grain shape 0.07μ) 0.2 Gelatin 1.2 Compound A 0.1 13th layer (high sensitivity blue-sensitive emulsion) Layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain shape 2.1)
μ) 1.8 Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 1.2)
μ) 0.5 Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 0.3
μ) 0.2 Fine grain silver iodobromide emulsion (average grain size 0.09μ) 0.2 Gelatin 1.2 Sensitizing dye VI 3 × 10 ^-4 Sensitizing dye VII 1 × 10 ^-4 Coupler C-6 0.3 Dispersion oil Oil-1 0.06 14th Layer (1st protective layer) Coupler C-7 0.1 UV absorber UV-1 0.05 Same as above UV-2 0.05 Same as above UV-3 0.05 Same as above UV-4 0.05 Same as above UV-5 0.05 Gelatin 0.6 Dispersion oil Oil-4 0.1 15th layer (Second protective layer) Gelatin 0.5 polymethylmethacrylate particles (diameter 1.5 μm) In each layer, a surfactant W-1 was added as a coating aid in addition to the above components. In addition, formalin scavenger was added.

The addition amount in the light-sensitive material is shown in grams per m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in a molar ratio with silver halide. It was

Compounds used in the examples This photosensitive material is referred to as Sample 001. Third for sample 001
Samples 002 and 003 were prepared by changing only the coating amount and the grain size of the silver iodobromide emulsions of the layers, the fifth layer, the seventh layer, the ninth layer, the eleventh layer and the thirteenth layer as shown in Table 1. .

These samples 001 to 003 were measured for sensitivity, fog, and graininess.

Sensitivity and fog were measured according to the method for measuring specific photographic sensitivity described in the text. For graininess, the same processing as the measurement of specific photographic sensitivity is performed, and the conventional RMS (Ro
ot Mean Square) method.

In addition, after manufacturing, the same treatment is performed after storing for 1 year,
An increase in fog and a decrease in sensitivity were observed.

Table 2 shows the measurement results of sensitivity, fog, and increase in fog after storage of graininess. However, the sensitivities, in addition to the photosensitivity: S described in the text, show the relative sensitivities when the sample 001 is set to 100 for each layer of blue, green, and red. RMS is 0.004 looks
The value with the exposure amount of second was shown.

As is clear from Table 2, the samples 002 and 003 of the present invention have a slightly lower sensitivity than the comparative sample 001, but this difference is not a problem in practical use, and graininess and fog increase during storage. It can be seen that is significantly improved.

Example 2 The order of layers was changed for Use 002 as follows.

1st layer Same as the 1st layer of Sample 002 2nd layer 〃 2nd layer 〃 3rd layer 〃 3rd layer 〃 4th layer 〃 9th layer 〃 5th layer 〃 4th layer 〃 6th layer 〃 5th layer 〃 7th layer 〃 6th layer 〃 8th layer 〃 7th layer 〃 9th layer 〃 8th layer 〃 10th layer 〃 11th layer 〃 11th layer 〃 12th layer 〃 12th layer 〃 13th layer 〃 1st layer 13th layer 〃 14th layer 〃 14th layer 〃 15th layer 〃 This sample is called sample 004. The sensitivity was measured in the same manner as in Example 1, and the results are shown in Table 3.

As is clear from Table 3, in Sample 004 having a layer arrangement different from that of the present invention, since the high-sensitivity red-sensitive emulsion layer was placed closer to the support, the sensitivity of the red-sensitive emulsion layer was lowered, which is not preferable.

Example 3 Samples 002 and 003 of the present invention were exposed and then processed using an automatic processor by the method described below (until the cumulative replenishment amount of the solution became 3 times the mother liquor tank capacity).

Next, the composition of the treatment liquid will be described.

<Color developer> <Bleaching solution> Common for mother liquor and replenisher solution Ethylenediaminetetraacetic acid ferric ammonium salt 120.0g Ethylenediaminetetraacetic acid secondary sodium salt 10.0g Ammonium nitrate 10.0g Ammonium bromide 100.0g Bleaching accelerator 5 × 10 ^-3 mol Ammonia water is added to pH 6.3 Water is added to 1.0 <bleach-fixing solution> Mother liquor and replenisher common ethylenediaminetetraacetic acid ferric ammonium salt 50.0 g Ethylenediaminetetraacetic acid disodium salt 5.0 g Sodium sulfite 12.0 g Ammonium thiosulfate 70%) 240m Ammonia water is added and pH 7.3 Water is added 1 <Wash water> Tap water is H type strong acid cation exchange resin (Mitsubishi Kasei Co., Ltd.)
Manufactured by Diaion SK-1B) and OH type strongly basic anion exchange resin (Diaion SA-10A). Sodium nourate 20 mg / was added.

Calcium ion 1.1mg / Magnesium ion 0.5mg / pH 6.9 <Stabilizer> Samples 002 and 003 of the present invention showed good results as in Example 1 even by this treatment.

Example 4 After exposing Samples 002 and 003 of the present invention to light, the following processing was performed.

The above-mentioned washing with water and the countercurrent washing with Hakara were adopted. Next, the composition after the treatment is described.

<Color developer> <Bleach> <Fixer> <Stabilizer> Samples 002 and 003 of the present invention were also treated by this treatment in Example 1,
Good results were obtained as in Example 3.

〔The invention's effect〕

As is clear from the above description, according to the present invention, a high-sensitivity color negative light-sensitive material of high image quality in which the increase of fog with time, the decrease of sensitivity, and the deterioration of graininess are prevented can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-60-55339 (JP, A) JP-A-60-156059 (JP, A) JP-A-60-128443 (JP, A) JP-A-59- 214853 (JP, A) JP 62-8146 (JP, A) JP 63-226651 (JP, A) JP 64-546 (JP, A) JP 60-194450 (JP, A) Japanese Patent Publication No. 4-17411 (JP, B2) Japanese Patent Publication No. 2-44051 (JP, B2) US Patent 3849138 (US, A)

Claims (1)

[Claims] 1. A support having a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler. And the specific photo sensitivity
In a color negative photographic material of 320 or more, the content of all silver contained in the photographic material is 3.0 g / m ^{2 to} 9.0 g / m ²
The red-sensitive emulsion layer, the green-sensitive emulsion layer, and the blue-sensitive emulsion layer are each composed of two or more emulsion layers having different sensitivities, and the red-sensitive emulsion layer having the highest sensitivity and the highest sensitivity At least one emulsion having a color sensitivity different from that of the highest sensitivity layer closest to the support between the support and the layer closest to the support among the green sensitivity emulsion layer and the most sensitive blue sensitivity emulsion layer. Layer is located and the most sensitive red sensitive emulsion layer,
The most sensitive green-sensitive emulsion layer and the most sensitive blue-sensitive emulsion layer each contain a 2-equivalent fast-reacting cyan coupler, a 2-equivalent fast-reactive magenta coupler, and a 2-equivalent fast-reactive yellow coupler. A silver halide color negative light-sensitive material characterized by: